EP0666292B1 - Überzugszusammensetzung und Überzugsfilmszusammensetzung - Google Patents

Überzugszusammensetzung und Überzugsfilmszusammensetzung Download PDF

Info

Publication number
EP0666292B1
EP0666292B1 EP95101628A EP95101628A EP0666292B1 EP 0666292 B1 EP0666292 B1 EP 0666292B1 EP 95101628 A EP95101628 A EP 95101628A EP 95101628 A EP95101628 A EP 95101628A EP 0666292 B1 EP0666292 B1 EP 0666292B1
Authority
EP
European Patent Office
Prior art keywords
coat layer
coating
titanium dioxide
coating composition
coating film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP95101628A
Other languages
English (en)
French (fr)
Other versions
EP0666292A2 (de
EP0666292A3 (de
Inventor
Ken Ohkura
Satoru Matsuzaki
Pekka Juhani Eskelinen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eckart Pigments Ky
Dainichiseika Color and Chemicals Mfg Co Ltd
Original Assignee
Eckart Pigments Ky
Dainichiseika Color and Chemicals Mfg Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eckart Pigments Ky, Dainichiseika Color and Chemicals Mfg Co Ltd filed Critical Eckart Pigments Ky
Publication of EP0666292A2 publication Critical patent/EP0666292A2/de
Publication of EP0666292A3 publication Critical patent/EP0666292A3/de
Application granted granted Critical
Publication of EP0666292B1 publication Critical patent/EP0666292B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/65—Chroma (C*)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/308—Total thickness of the pigment particle
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/259—Silicic material

Definitions

  • This invention relates to coating compositions and coating film compositions.
  • Usual exterior coating compositions for four- and two-wheel vehicles are roughly classified into solid coatings and metallic coatings.
  • the solid coatings are prepared by adding a colored pigment, e.g., copper phthalocyanine pigment, quinacridone pigment, perillene pigment, etc. to a coating film.
  • a colored pigment e.g., copper phthalocyanine pigment, quinacridone pigment, perillene pigment, etc.
  • aluminum or like metal powder or mica pigment is usually used together with the colored pigment noted above for the purpose of providing a sense of brightness.
  • the coating films formed by using the above solid and metallic coatings are required to have sufficient durability for protecting the base as well as ornamental character (i.e., aesthetic character).
  • ornamental character i.e., aesthetic character
  • recent needs for attaching importance to the peculiarity of vehicles and the like are reflected by strong demands for diversification of coating films with respect to the color, ornamentality (aesthetic property), etc. of the top coat.
  • Titanium dioxide particles which are a typical white pigment, have heretofore been applied to many coating compositions because of excellent whiteness and concealing and weather - proof properties. Also, to meet recent coat color diversification demands there are coat color proposals which use far finer titanium dioxide particles compared to the conventional titanium dioxide particles. However, there is no example of study of variations of the coat color sense with particle shape variations. As a sole exception, titanium dioxide coat mica pigment is a pigment shape variation. This pigment, however, is mainly composed of mica, and therefore its coating films inevitably have reduced hiding property and color attachment power. In addition, in shelf time it sinks greatly because its particle diameter and weight are large.
  • the invention accordingly has an object of providing a coating composition and a coating film composition, which permits formation of a coating film having a characteristic directivity in high brightness (high whiteness) coat color, permits the quality sense of a mica pigment coating film based on a three - coat two - bake coating process with a coating film based on a two - coat one - bake coating process, and permits, when used together with a colored pigment, obtaining a coating film having mild color changes from highlight to shade.
  • the above object of the invention is attained by a coating composition according to claim 1.
  • the titanium dioxide pigment being in the form of flaky small pieces of silicon dioxide covered by titanium dioxide and having a diameter of 1 to 300 microns and a thickness of 0.01 to 1 micron is hereinafter referred to as flaky titanium dioxide; a considerable portion of the silicon dioxide being dissolved out from the titanium dioxide - coated silicon dioxide small pieces.
  • a coating composition which is white in color, has directivity in light reflection and does not sink greatly during shelf time, and found that the intention is met by a coating composition, containing a titanium dioxide pigment having a specific shape, i.e., flaky titanium dioxide.
  • the coating composition of the invention is obtainable by forming a colored base coat layer on a substrate by using the above coating composition and then forming a clear coat layer on the colored base coat or by forming a colored base coat layer as a first layer on a substrate, then forming a second colored base coat layer on the first base coat by using the above composition according to the invention and then coating a clear coat layer.
  • the flaky titanium dioxide used according to the invention may be surface - treated as is well known in the art (EP-A-0377326).
  • it may be those commercially available under trade names of "TS - 10" and "PS - 10" (KEMIRA Inc., Finland).
  • the flaky titanium dioxide pigment noted above is in the form of flaky small pieces of silicon dioxide covered by a titanium dioxide and having a diameter of 1 to 300 microns and a thickness of 0.001 to 1 micron, with a considerable portion, i.e., 20 to 90 % by weight, of the silicon dioxide being dissolved out from the titanium dioxide - coated silicon dioxide small pieces. According to the invention, it is particularly desirable to use flaky titanium dioxide with a diameter of 10 to 60 microns and a thickness of 0.01 to 0.5 micron.
  • the coating film which is formed by coating the coating composition on a substrate has the following excellent features not possessed by coating films obtainable from the prior art coating compositions.
  • coloring pigment used together with the flaky titanium dioxide may be used colored pigments used for usual coating. Its specific examples are copper phthalocyanine pigment, quinacridone pigment, perillene pigment, anthraquinone pigment, metal complex pigment, transparent iron oxide pigment and carbon black.
  • the metal powder pigment used according to the invention may be aluminum powder, copper powder, stainless steel powder. Among these pigments, aluminum powder is used most usually.
  • mica pigment may be used those well known in the art. Its examples are transparent pearl mica, colored mica, interference mica, etc.
  • the coating film formation resin used according to the invention may be used those well known in the field of the coating. Its examples are acrylic acid resin, acrylmelamine resin, vinyl chloride - vinyl acetate resin, alkyd resin, polyester resin, polyurethane resin and amino resin. These examples of the coating film formation resin which can be used according to the invention are by no means limitative.
  • organic solvent for dissolving or dispersing the coating film formation resin may be used those well known in the art. Its examples are toluene, xylene, butyl acetate, methyl acetate, acetone, methylethyl ketone, methanol, ethanol, butanol and cyclohexane.
  • the flaky titanium dioxide is used in an amount of 0.005 to 50 parts by weight, preferably 1 to 30 parts by weight, with respect to 100 parts by weight of the coating composition. If the amount is less than 0.005 part by weight, it is impossible to obtain the coating composition intended according to the invention. If the amount exceeds 50 parts by weight, on the other hand, the physical properties of the coating film are undesirably reduced although it is possible to obtain the coating composition intended according to the invention.
  • the amount of each of the colored, mica and metal powder pigments that may be incorporated according to the invention is 1.0 to 30 parts by weight with respect to 100 parts by weight of the coating composition.
  • the total amount of one or more members of the group consisting of the colored, mica and metal powder pigments is 0.01 to 10,000 parts by weight with respect to 100 parts by weight of the flaky titanium dioxide.
  • the coating composition intended according to the invention cannot be obtained.
  • the coating composition of the invention may, if necessary, incorporate fillers, anti-charging materials, stabilizers, anti-oxidation agents, ultraviolet radiation absorbers.
  • the coating composition of the invention may be prepared by adding the flaky titanium dioxide pigment and, if necessary, one or more pigments selected from the group consisting of the colored, mica and metal powder pigments to an organic solvent solution of the coating film formation resin and then stirring the mixture by using a sand mill or a high speed stirrer.
  • the coating composition obtained in this way is coated by spray coating, electrostatic coating, flow coating, roll coating, on a substrate, e.g., a metal substrate, a glass substrate, a plastic substrate, etc., provided with a base treatment if necessary, followed by drying and cross-linking hardening to obtain a colored coat layer.
  • a substrate e.g., a metal substrate, a glass substrate, a plastic substrate, etc.
  • the colored coat layer as a base coat layer and coat on this base layer a clear coat material, which is prepared by dissolving or dispersing a resin like the coating film formation resin noted above in an organic solvent, followed by drying and a subsequent heat treatment to obtain the coating film.
  • the coating composition of the invention is prepared by preliminarily preparing a base coating by adding the flaky titanium dioxide and colored, mica and metal powder pigments separately to an organic solvent solution containing the coating film formation resin and mixing a predetermined amount of each base coating.
  • the coating film obtainable by coating the coating composition of the invention on the substrate is excellent in the hiding property and also excellent in the ornamental property in that a directivity can be obtained even in a high whiteness (brightness) region.
  • the flaky titanium dioxide reflects more white light, while the sense of brightness is increased.
  • the white light reflection decreases a little, and the L value becomes smaller, however, it is still permitting obtaining a coating film having sufficient whiteness (L value) for emphasizing the white coat color.
  • L value whiteness
  • the flaky particles as the flaky titanium dioxide are very thin, even if their content in the coating film is high, the surface smoothness therefore is not lost, and it is possible to obtain a coating film having an excellent finish. This merit can solve the problem posed with the conventional flaky particles.
  • the titanium dioxide coated mica is inferior in the hiding property and color attachment power, although it can satisfy the coating film quality sense with respect to the directivity.
  • it permits difficult coat color design of the two-coat one -bake coating film in the high whiteness (i.e., high brightness) region.
  • the whiteness in the shade region is reduced although the sense of brightness can be satisfied.
  • the incorporation of the flaky titanium dioxide and one or more pigments selected from the group consisting of the colored, mica and metal powder pigments in the coating composition permits diversification of the coat color and ornamentality, particularly provision of variations of the quality sense of the coating film, it is possible to obtain further pronounced effects as follows.
  • the sense of coat color which cannot be expressed by incorporating the prior art brightness material (i.e., metal powder pigments and various mica pigments) and colored pigment. More specifically, the sense of the coat color based on the ordinary brightness material and colored pigment, light reflection is very high as an optical characteristic in the neighborhood of positive reflected light. The high light reflection is susceptible by the man's eyes as a "sense of glitter". In the shade region, light reflected from the ordinary brightness material is reduced, and therefore scattered reflected light from the colored pigment predominates.
  • the prior art brightness material i.e., metal powder pigments and various mica pigments
  • the difference in light component between the positive and negative reflected light regions is pronounced.
  • the flip -flop between these two regions and the light intensity difference in the positive reflected light region govern the quality sense of the coating film containing the brightness material.
  • the difference in the light component between the positive and negative reflected light regions is somewhat mild, and also the light intensity difference in the positive reflected light region is mild. It is a featuring aspect, on the other hand, that the color change in the negative reflected light region is great compared to the coating film containing the ordinary brightness material. This effects comes from the strong performance of the flaky titanium dioxide particles as a coloring material in the coating film.
  • a further function to be added concerns the problem of sedimentation of pigment during the shelf time.
  • the flaky pigment sinks during the shelf time because of its large particle diameter and heavy weight. In most cases, this problem is solved by the use of an anti-sinking agent.
  • the coating composition of the invention is less subject to sinking during the shelf time of the coating, which is a great feature of the invention.
  • Components of coating composition of the invention amounts (parts) Flaky titanium dioxide (TS-10) 30 parts Acrylic varnish (solid part : 60 %) 82 parts Melamine varnish (solid part : 60 %) 34 parts Solvesso 100/butyl acetate (7/3) mixed solvent 30 parts
  • Components of coating composition of the invention amounts (parts) Flaky titanium dioxide (PS-10) 30 parts Acrylic varnish (solid part : 60 %) 82 parts Melamine varnish (solid part : 60 %) 34 parts Solvesso 100/butyl acetate (7/3) mixed solvent 30 parts
  • Components of coating composition of the invention amounts (parts) Flaky titanium dioxide (TS-10) 15 parts Titanium dioxide (CR - 97) (manufactured by Ishihara Sangyo)) 15 parts Acrylic varnish (solid part : 60 %) 82 parts Melamine varnish (solid part : 60 %) 34 parts Solvesso 100/butyl acetate (7/3) mixed solvent 30 parts
  • Components of coating composition of the invention amounts (parts) Flaky titanium dioxide (TS-10) 28 parts Copper Phthalocyanine Blue 5206 (manufactured by Dainichiseika Kogyo) 2 parts Acrylic varnish (solid part : 60 %) 82 parts Melamine varnish (solid part : 60 %) 34 parts Solvesso 100/butyl acetate (7/3) mixed solvent 30 parts
  • Contrast Example 3 a base coat is formed with the coating material used in Contrast Example 1, and "Pearl White” used in Contrast Example 2 was coated to 2 to 5 microns as a second layer.
  • compositions of Contrast Example amounts (parts) Aluminum Pigment 7620NS (manufactured by Toyo Arumi) 28 parts Copper Phthalocyanine Blue 5206 2 parts Acrylic varnish (solid part : 60 %) 82 parts Melamine varnish (solid part : 60 %) 34 parts Solvesso 100/butyl acetate (7/3) mixed solvent 30 parts
  • the coating materials in the above Examples 1 to 4 and Contrast Examples 1 to 4 were diluted with a thinner to a spray viscosity (14 seconds with Ford cup No. 4) and then coated by spraying on treated steel panels using an air spray gun. After 10 minutes of drying, clear (acrylic melamine) coating was made with an air spray gun. Further, after 15 minutes of drying at room temperature, the samples were hardened by baking at 140°C for 30 minutes, thus obtaining steel panels.
  • the geometrical metamerism of the coating film was shown in terms of measured values of changes in the brightness and chromaticity for various light reception angles with a fixed light incidence angle. Hiding property is also measured in film thickness.
  • chromaticity and brightness were measured by receiving at four different light reception angles of -70° , -30° , +10° and +40° with the light incidence angle fixed at -50° and the quality sense of the coating film was evaluated.
  • each coating composition noted above was spray coated on a panel coated in separate white and black colors, and the property was evaluated in terms of the thickness of dried and hardened film upon reaching of a film thickness, with which the boundary between the base white and black colors could no longer be determined.
  • Result of measurement Hiding property Light reception angle L * value C * value Ex. 1 45 ⁇ m -70° 89 2.3 -30° 92 2.4 +10° 98 2.7 +40° 119 2.6
  • Ex. 2 65 ⁇ m -70° 85 2.4 -30° 89 2.3 +10° 100 2.7 +40° 135 2.9
  • Ex. 3 26 ⁇ m -70° 90 2.1 -30° 92 2.5 +10° 98 2.6 +40° 112 2.4
  • the coating composition of the invention permits formation of a coating film, which has a characteristic directivity in high brightness (or high whiteness) coat color. Also, it is possible to obtain a quality sense of a three -coat two-bake coating process coating film based on mica pigment by two-coat one bake process incorporating flaky titanium dioxide pigment.
  • coating film incorporating a colored pigment it is possible to obtain coat color with mild color changes as changes from highlight to shade.
  • a particular feature is a coating film having geometrical metamerism in a shade region.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Silicon Compounds (AREA)

Claims (6)

  1. Beschichtungszusammensetzung, umfassend ein flüssiges Medium, das ein Titandioxidpigment und ein filmbildendes Beschichtungsharz umfaßt, wobei das Titandioxidpigment sich auf 0,005 bis 50 Gewichtsteile, bezogen auf 100 Gewichtsteile der Beschichtungszusammensetzung, beläuft und in Form von flockenförmigen, kleinen, mit Titandioxid bedeckten Siliziumdioxidteilchen vorliegt und einen Durchmesser von 1 bis 300 Mikrometer und eine Dicke von 0,001 bis 1 Mikrometer aufweist, wobei 20 bis 90 Gewichtsprozent des Siliziumdioxids aus den kleinen mit Titandioxid beschichteten Siliziumdioxidteilchen herausgelöst sind.
  2. Beschichtungszusammensetzung nach Anspruch 1, die weiterhin mindestens ein Pigment enthält, ausgewählt aus der Gruppe, bestehend aus organischen Beschichtungspigmenten (beispielsweise Phthalocyaninpigmenten, Chinacridonpigmenten, Perillenpigmenten, usw.), anorganischen Pigmenten (beispielsweise Titandioxid, Eisenoxiden usw.), Aluminiummetallicpigmenten und Glimmerpigmenten.
  3. Beschichtungsfilmzusammensetzung, umfassend eine Grundbeschichtung, gebildet auf einem Substrat und umfassend die Beschichtungszusammensetzung nach Anspruch 1 und eine klare Beschichtung, gebildet auf der Grundbeschichtung.
  4. Beschichtungsfilmzammensetzung, umfassend eine gefärbte Grundbeschichtung, gebildet auf einem Substrat und umfassend die Beschichtungszusammensetzung nach Anspruch 2 und eine klare Beschichtung, gebildet auf der gefärbten Grundbeschichtung.
  5. Beschichtungsfilmzusammensetzung, umfassend eine gefärbte Grundbeschichtung, gebildet auf einem Substrat, eine zweite Grundbeschichtung, gebildet auf der gefärbten Grundbeschichtung und umfassend die Beschichtungszusammensetzung nach Anspruch 1 und eine klare Beschichtung, gebildet auf der zweiten Grundbeschichtung.
  6. Beschichtungszusammensetzung, umfassend eine erste gefärbte Grundbeschichtung, gebildet auf einem Substrat, eine zweite gefärbte Grundbeschichtung, gebildet auf der ersten gefärbten Grundbeschichtung und umfassend die Beschichtungszusammensetzung nach Anspruch 2 und eine klare Beschichtung, gebildet auf der zweiten gefärbten Grundbeschichtung.
EP95101628A 1994-02-07 1995-02-07 Überzugszusammensetzung und Überzugsfilmszusammensetzung Expired - Lifetime EP0666292B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP33282/94 1994-02-07
JP06033282A JP3123697B2 (ja) 1994-02-07 1994-02-07 塗 膜
JP3328294 1994-02-07

Publications (3)

Publication Number Publication Date
EP0666292A2 EP0666292A2 (de) 1995-08-09
EP0666292A3 EP0666292A3 (de) 1997-01-02
EP0666292B1 true EP0666292B1 (de) 1999-09-08

Family

ID=12382185

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95101628A Expired - Lifetime EP0666292B1 (de) 1994-02-07 1995-02-07 Überzugszusammensetzung und Überzugsfilmszusammensetzung

Country Status (4)

Country Link
US (1) US5554439A (de)
EP (1) EP0666292B1 (de)
JP (1) JP3123697B2 (de)
DE (1) DE69511914T2 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4034365B2 (ja) * 1995-03-09 2008-01-16 大日本印刷株式会社 超微粒子含有反射防止フィルム、偏光板及び液晶表示装置
ES2252939T3 (es) * 1998-04-15 2006-05-16 Basf Coatings Japan Ltd. Metodo para la formacion de una pelicula de recubrimiento y composicion del recubrimiento.
JP2000086943A (ja) * 1998-09-10 2000-03-28 Nippon Paint Co Ltd ２色性塗料組成物
US6368399B1 (en) 1999-07-21 2002-04-09 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Composite pigments, coloring compositions, and image recording substances
US6849310B2 (en) 2001-04-20 2005-02-01 Schlegel Corporation Contiguous colliquefaction forming a surface film for a composite strip
WO2004113455A2 (en) * 2003-06-17 2004-12-29 Ciba Specialty Chemicals Holding Inc. A process for the preparation of a pigment comprising a core material and at least one dielectric layer
JP4751043B2 (ja) * 2004-09-21 2011-08-17 関西ペイント株式会社 複層塗膜形成方法及び塗装物品
US20060177627A1 (en) * 2005-02-09 2006-08-10 Schlegel Corporation Carrier assembly with fused power and frame-warp aperture
JP2011026543A (ja) * 2009-06-22 2011-02-10 Kansai Paint Co Ltd 塗料組成物及び塗膜形成方法
JP2011025101A (ja) * 2009-07-21 2011-02-10 Nippon Paint Co Ltd 光輝性複層塗膜の形成方法
JP5478992B2 (ja) * 2009-08-28 2014-04-23 日本ペイント株式会社 複層塗膜形成方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4499143A (en) * 1983-08-26 1985-02-12 Inmont Corporation Multilayer automative paint system
JPS61107979A (ja) * 1985-08-13 1986-05-26 Nissan Chem Ind Ltd 滲出による着色汚損を防止する方法
US4753829A (en) * 1986-11-19 1988-06-28 Basf Corporation Opalescent automotive paint compositions containing microtitanium dioxide pigment
US4849283A (en) * 1987-07-16 1989-07-18 Ppg Industries, Inc. Composite coatings employing polyepoxides and polyacid curing agents in base coats
JPH01185373A (ja) * 1988-01-21 1989-07-24 Tokuyama Soda Co Ltd シリカおよびその製造方法
FI85157C (fi) * 1988-12-28 1992-03-10 Kemira Oy Foerfarande foer framstaellning av ett transparent metalloxidpigment.
IL92372A0 (en) * 1989-11-20 1990-07-26 Israel State Coatings for greenhouses and the like
JPH05194882A (ja) * 1992-01-21 1993-08-03 Teika Corp メタリック塗料組成物
JPH0633282A (ja) * 1992-07-15 1994-02-08 Mitsubishi Heavy Ind Ltd 固体電解質電解セル
DE4322997A1 (de) * 1993-07-09 1995-01-12 Merck Patent Gmbh Offset-Druckfarbe
US5376698A (en) * 1993-09-21 1994-12-27 The Mearl Corporation Polyolefin compositions containing coated mica particles to prevent yellowing and methods therefore

Also Published As

Publication number Publication date
EP0666292A2 (de) 1995-08-09
US5554439A (en) 1996-09-10
JPH07224235A (ja) 1995-08-22
JP3123697B2 (ja) 2001-01-15
DE69511914T2 (de) 1999-12-23
DE69511914D1 (de) 1999-10-14
EP0666292A3 (de) 1997-01-02

Similar Documents

Publication Publication Date Title
US4814208A (en) Finish coating method
US5871827A (en) Finishes containing light interference pigments
US4937274A (en) Coating composition
EP0404378B1 (de) Überzugsmischung
JPS63183965A (ja) 塗装組成物
JPH0517710A (ja) メタリツク塗料とその塗装法
EP0666292B1 (de) Überzugszusammensetzung und Überzugsfilmszusammensetzung
JP4233669B2 (ja) ストレートシェードコーティング組成物
US3283036A (en) Non-reflective coating composition containing finely divided polypropylene
AU725889B2 (en) Finishes containing light interference pigments
US5017638A (en) Metallic paint film
JP3159884B2 (ja) 塗料組成物及び塗膜形成方法
JPH08170034A (ja) メタリック塗料組成物および塗膜形成方法
EP0319918B1 (de) Methode zum Auftragen eines metallischen Überzuges
JPS62210081A (ja) 真珠光沢顔料含有塗料のコ−テイング方法
JP3386222B2 (ja) 意匠塗膜形成方法
EP0439107A1 (de) Laminargraphit enthaltende Pigmentzusammensetzung
JP3370204B2 (ja) 光輝性塗膜形成方法
JPH101625A (ja) 塗料組成物、塗膜形成方法及び塗装物
JP2001226612A (ja) 金属調塗料組成物、塗膜形成方法および塗装物
JP2701888B2 (ja) 被覆用組成物及びそれを用いた複層塗膜形成方法
JP2001207129A (ja) 光沢性塗料及び光沢性塗膜の形成方法
JPH08243481A (ja) 干渉性塗膜形成方法
JP2001191020A (ja) 発色性に優れたメタリック塗装及びメタリック塗装物
JPH0768215A (ja) 塗装仕上げ法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE FR GB IT

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB IT

17P Request for examination filed

Effective date: 19970225

17Q First examination report despatched

Effective date: 19970520

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ECKART PIGMENTS KY

Owner name: DAINICHISEIKA COLOR & CHEMICALS MFG. CO. LTD.

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 69511914

Country of ref document: DE

Date of ref document: 19991014

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20140217

Year of fee payment: 20

Ref country code: FR

Payment date: 20140211

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20140206

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20140417

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69511914

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69511914

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20150206

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20150206